Method of and apparatus for treating waste pickle liquor



, E. W. D. LAUFER AND E. VON WINTZINGERODE.

A. T.-WEAVER METHOD OF AND APPARATUS FOR TREATING WASTE PICKLE LIQUOR.

APPLICATION LED AUG-3. I9I6.

Patented Aug. 3

2 SHEETS-SHEET I.

N NN PATENT OFFICE.

ALBERT T. WEAVER, 0F JOLIET. ERNEST W. D. LAUFER. OF ARLINGTON HEIGHTS, AND EBERHARIJ VON WINTZINGERODE, OF CHICAGO. ILLINOIS. ASSIGNORS TO THE AMERICAN STEEL & WIRE COMPANY OF NEW JERSEY, 0F HOBOKEN, NEW JERSEY, A CORPORATION OF NEW JERSEY.

METHOD OF AND APPARATUS FOR TREATING WASTE PICKLE LIQUOR.

Application filed August 3, 1916.

To all whom it may concern I 1 Be it known that we, ALBERT 'l VI'IAYI'IR,

a citizen of the United States. and resident of Joliet, in the county of ill and State of Illinois, Ilnxnsr \V.- D. LAUFER, a citizen of the I nited States. and resident of Arlington Heights, in the county of .Cook and State of Illinois. and EBl-IRILUH) voN \ViN'rzrNoERonn, a subjectof the Emperor of Germany, and resident of Chicago. in the county of Cook and State of Illinois. have invented certain new and useful lnr provements in Methods of and Apparatus for Treating \Vaste Pickle Liquor, of which the following is a specification.

the method. However, said application in cluded a furnace or retort similar to the one herein disclosed and covered the full details thereof. This application includes the retort of the earlier application and the method therein disclosed.

In sheet, plate, wire mills and other establishments in which steel is produced in its different forms, it is customary to' clean or pickle the articles either prior to or after being subjected to treatments-such as galvanizing; tinning, etc. This treatment consists in immersing the article in a bath of weak sulfuric acid. As a result, the bath becomes weakened, due to the formation of soluble sulfates therein, and the bath must be renewed at intervals. The problem in large mills is twofold: first, as to a method of disposing of this waste liquor. It is Specification of Letters Patent.

Serial No. 112.898.

contrary to Government laws to discharge the liquor into flowing streams because of the presence of a sullicient quantity of free acid to contaminate water and act upon metal work in the streams; second, the problem is presented as to a means for saving the relatively large quantity of iron oxid and sulfuric acid. Some of the acid is free. but the larger portion thereof is combined in the form of sulfates.

We are aware that mahy methods have been proposed for treating the soluble sulfates analytically in order to separate the elements. but all the methods with which we are acquainted are subject to many 0bjections.

()ne of the principal objects of the present method and apparatus is to provide a continuous process which may be carried out without interruption and which shall ha re ample capacity A further object is in the provision of means whereby the conversion operations may be carried out in a zone apart from thc'path of the products of combustion, to the end that the by-products may be free of foreign matter. such as free carbon, carbon monoxid. carbon dioxid, etc.

It is, we believe, fundamental that in order to separate a compound into its ele- Patented Aug. 3, 1920.

ments it is necessary to supply at least as great an amount of heat as was evolved in the synthetical reaction in which the compound was formed. Not only is this true, but in the present instance because of the fact that the compound is diluted with a.

which we refer is more in the nature of an atomization, it being necessary that the liquid shall be subdivided into practically similar devices which require heat. Weprer.

its molecular relation, and to than; end we fer also to provide an auxiliary grate 28, have devised a spray nozzle by eans of by means of which additional heat may be which the liquor is supplied to t e cham-- supplied to the catalyzer if necessary. The her under air pressure in the form, of a specific form of the catalyzer forms no part heavy vapor or mist. g of our invention. 6 1 I The method and apparatus will be more The vapors leave the catalyzer at the readily understood by reference to the acupper end and pass through the pipe 28 to companying drawings, wherein Figure 1 is a vertical section through a plant constructed in accordance with our invention', the illustration .being somewhat diagrammatic in form;

Fig. 2 is an enlarged vertical section through the conversion furnace, the view taken at right angles to that of Fig. 1 and Fig. 3 is an enlarged view of one of the nozzles employed. a

.The conversion furnace is mounted upon a suitable foundation and comprises brick walls 10 and a' suitable metal lining 11.

, the acid condenser D.

his device is of simple construction and serves to combine the sulfur trioxid delivered from the catalyzer with the steam, and change the sulfurous acid to sulfuric acid. It consists of a cast iron lead-lined cylindrical shell 29 having an inlet 30 for'the vapors. iron shell is surrounded by a lighter shell 31 forming a jacket. between the walls within which cold water is circulated. At the bottom of the chamber we provide a perforated lead plate 32, through which the condensed vapors, now in the form of-acid,

end of the catalyzer shell.

Grates 12 are placed inthe lower portion ,may trickle,'falling upon a quantity of stone of the furnace. Combustion takes place 33, held within a vitreous casing 34, the above the grate and the products of, comlower portion of which is seated in and bustion pass upwardly through the space sealed by a lead-lined tank 35. The acid 13 to the outlet 14. An inverted V-shaped may be removed through the outlet 36, or floor 14 is provided in the furnace upon may be returned through the condenser by a which iron oxid is deposited and from suitable circulating pump, for the purpose which the same falls into the spaces 15. of increasing the strength of the finished At the bottom of the spaces we provide two acid. conveyers 16, by means of which the ox-id v We have shown in the drawings and have is removed, either continuously or at indescribed the use of a catalyzer through tervals. Y which the vapors pass in the passage thereof The roof 17 of the furnace is likewise of from the retort to the condenser. Wev do metal and is provided with a plurality of not'rely on the use'of the catalyzer for the apertures within which nozzles are mounted, carrying'out of our invention. The use of a such as shown in detail in Fig. 3 and which catalyzer is well known and in our method will be specifically described hereinafter. we' use it merely for the'purpose of hasten- At a point near the lower end'of the furing the oxidation of sulfurous gases to sulnace we provide a plurality of outlets 18, furic; It is by no means essential that a covered by suitable baflles 19, through which catalyzer be used, and we do not wish to be r The cast the vaporous' .products of the reaction esunderstood as limiting our invention to such cape. It has been found that all of the an apparatus wherein a catalyzer. is an esvapors may be'allowed to pass out through sential part and'ainethod depending on the apertures near the lower end of the furnace 'action of a catalyzer for its functioning.

and all of such vapors caused to pass The spray nozzles, such asshown in Fig.

the openings 18 to a main 21, by means of tobe seated in the apertured lugs formed in which the vapors are conveyed tothe lower the; top of the furnace and are provided i with an annular. flange 38, by means of 'The catalyzer is containedwithin a cham- "which the nozzleis bolted to the'fiange of. her formed by the walls 22 and consists of a thelug. Walls are provided in the tubular shell 23 containing a'quantity of iron oxid, portion37, whereby the space is, divided into indicated. at 24, preferably in the form of a water container 39 and an air conduit 40, lumps or nodules' We may prefer to use A small tube 41 is interposed in the air 'latinized asbestos instead of the, iron oxid. space, and the liquor is adapted to be supt will be understood that in this device the plied to this tube at the inlet; 42. A con- S0 is converted into S0 The chamber nection 43 provides also for the entrancewithin which the shell is mounted is 'conof air to the liquorconduit, and the entrance nectedwith the flue 14 from the furnace and 44 provides for the supply of air to the the products of combustion are caused to space 40. The extreme upper end of the pass around the catalyzer; thence out -nozzle is closed by a stuffing box 45, which through the flue 25 to the stack 26, or to the I conduit 27 which may lead to bakers or insertion of a pointed wire, this wire to be.

,may beremovedor loosened to permit the 110 through the catalyzer. Conduits 2 0 connect 3, comprise a tubular portion 37, adapted 4 directed to the contracted exit opening 46, which may become clogged after continued operation. By the use ofthe nozzle described, we are enabled to spray the liquor into the furnace in practically its molecular relation, the mechanical sub-division being so fine as to give the appearance of a fog or mist.

The liquor to be treated is storedin the tank B and is removed therefrom by the pump 47 and delivered to the nozzle in the top of the furnace, air being supplied at suitable pressure as required.

The operation of the method is as follows: Assuming a supply of liquor in the tank B, the fires are started on the grates 12 of thefurnace, and, when the furnace is sufliciently heated the nozzles at the upper portion of the furnace are turned on and the operation begins. It is intended that the temperature in the upper portion of the furnace shall be approximately 1200 F., and at the lower portion approximately 1500 F. Immediately upon the entrance of the liquor into the temperature described, it is vaporized, the water being changed into the form of steam, the acid fumes descending and becoming more highly heated as they descend. The analytical reaction then begins and the sulfate is broken up, forming sulfur dioxid and sulfur trioxid, the iron oxid being released. The sulfurous and sulfuric acid gases thus formed and the steam pass out through the openings 18 and are directed into the catalyzer, where the sulfur dioxid is transformed into sulfur trioxid, and the sulfurous acid to sulfuric, the temperature maintained in the catalyzer being between 800 and 1000 F.

The vapors after leaving the catalyzer are conducted to the condenser where the acid gases combine with the steam and are condensed to form sulfuric acid. The iron oxid which is deposited in the furnace has been found to be of an exceedingly high quality, this result being secured, undoubtedly,by the freedom from deleterious or contaminating substances which are ordinarily found in products of combustion. The reaction taking place in a closed chamber, the chemicals do not come in contact with any of the waste products of combustion. The resultant recovery of iron oxid is, therefore, of considerable value for pigments over that ordinarily produced, being naturally in an impalpable state of division without grinding. It will be seen that the process is continuous and that once having started the plant it s operation becomes simple requiring but little attention other than that of maintaining the proper temperatures.

The process has, after a series of tests, been found to o'perate in the manner described and to produce sulfuric acid and iron oxid in a most eflicient manner. While the steps described will be followed preferably as herein described, it is possible to vary such steps to a certain extent and to modify the apparatus to a still greater extent, all without departing from the spirit of our invention.

.VVe claim:

1. In a method of treating a pickle liquor solution including certain sulfates in water and recovering sulfurous and sulfuric acld gases and oxids, the steps of spraying the solution in a finely divided condition into a furnace, conducting the evolved water and sulfurous and sulfuric acid gases from the furnace,.condensing the vapors in the presence ofsteam and depositing the oxid on the floor of the furnace, substantially as described.

2. In apparatus for treating waste pickle liquor, the combination of a retort, means for heating the walls of said retort to an ex tent sufficient to cause a breaking up of or chemical reaction in the matter being treated, means for atomizing the liquid to be treated into the retort, a condenser, means for conductingthe gases and vapors from the retort to said condenser, thelower portion ofsaid retort being formed to receive the solid residue from the reaction, substantially as described.

3. In a method of treating waste pickle liquor, the steps of atomizing the liquor into a retort having a temperature of 1200 to 1500 F., whereby a chemical reaction takes place, depositing the evolved oxid on the floor of the retort, conducting the evolved sulfurous and sulfuric acid gases from the retort and condensing the same in the presence of water.

4:. In an apparatus for treating waste pickle liquor, the combination of a retort, means for generating heat by a flame exteriorly thereof whereby a temperature of substantially 1200 degrees F. is maintained within saidretort, means for spraying sulfate in solution into said retort, means for conveying away the volatile constituents of the liquor and permitting the deposition of the oxid on the floor of the retort, 'substan- I 6. 'l he method of treeting waste pickle Signed at Chicago, Illinois this 27th day 16 .liquor solution to recover the constituents of July, A. D. 1916. thereof, which consists in subjecting said solution in ntomized form to heat whereby the oxid is recovered in a solid state, withv EBERHARD' MNTZI'NGEBODE' drawing the evolved gases from said retort v and condensing the same whereby any sul-- Witnesses:

furous acid may become sulfuric acid-on ex- JAMES E. SIME posnre to the atmosphere. MADELEINE R. bAREL. 

